JP2000281863A - Resin composition and its cured material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition having excellent coating performance and capable of forming a coating film having excellent hardness, scratch resistance, low curling tendency, adhesivity, transparency and appearance of coating surface especially free from ripple mark, streak, uneven coating, cissing, etc., on the surface of various substrates and provide a cured article of the resin composition. SOLUTION: The objective resin composition contains (A) particles produced by bonding oxide particles of at least one kind of element selected from silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium to a specific organic compound containing a polymerizable unsaturated group and a group expressed by formula [X is NH, O(oxygen atom) or S(sulfur atom); Y is O or S], (B) a compound containing >=2 polymerizable unsaturated groups in the molecule and (C) at least two kinds of organic solvents having different relative evaporation speeds. The difference between the maximum value and the minimum value of the relative evaporation speed of the organic solvents is >=1.5.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a resin composition and a cured product thereof. More specifically, it has excellent coatability and various substrates [for example, plastics (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, triacetyl cellulose, ABS resin) , AS resin, norbornene-based resin, etc.), metal, wood, paper, glass, slates, etc.], hardness, scratch resistance, low curl, adhesion, transparency and appearance of the coating surface, especially The present invention relates to a resin composition capable of forming a coating film (film) having excellent appearance and a cured product thereof. The resin composition of the present invention and a cured product thereof are, for example,
Plastic optical parts, touch panels, film-type liquid crystal elements, plastic containers, floor materials as building interior materials, wall materials, protective coating materials for preventing marring (scratching) and contamination of artificial marble; various base materials Adhesives, sealing materials, and binder materials for printing ink.

[0002]

2. Description of the Related Art In recent years, protective coating materials for preventing scratches (scratch) and contamination of various substrate surfaces; adhesives and sealing materials for various substrates; binder materials for printing inks; A resin that has excellent coating properties and is capable of forming a coating on the surface of various substrates that is excellent in all of hardness, scratch resistance, low curl, adhesion, transparency, and appearance of the coating surface There is a need for compositions. Among these requirements, various materials containing colloidal silica as particles to be contained therein have been proposed with the aim of improving scratch resistance. For example, U.S. Pat. No. 3,451,838 and U.S. Pat.
Japanese Patent No. 404,357 discloses that a composition mainly composed of a hydrolyzate of alkoxysilane and colloidal silica is used as a thermosetting coating material. Also, for example, Japanese Patent Publication No. Sho 62-21815,
A composition of acrylate and particles obtained by modifying the surface of colloidal silica with methacryloxysilane is coated with a photocurable core.
It is disclosed to be used as a coating material. The feature of these coating materials is that the surface of the silica particles is treated with a specific organosilane or specific conditions to improve the performance of the coating material. However, such a coating material has excellent coatability as a resin composition, and excellent hardness, scratch resistance, low curl, adhesion, transparency, and coating when formed into a cured film. Not all of the appearances of the film surface were necessarily satisfactory. In particular, with the improvement in productivity of coated products in recent years, improvements in production equipment such as improvement in production line speed, increase in air blowing speed during coating film drying, and increase in drying temperature have been implemented. When used, poor appearance of the coating surface such as wind ripples, streaks, uneven coating, and repelling may occur.

[0003]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and has excellent coating properties, and has hardness, abrasion resistance, and low curl properties on the surface of various substrates. Adhesiveness, transparency and appearance of the coating surface, particularly, a resin composition capable of forming a coating excellent in the appearance of the coating surface without wind ripples, streaks, coating unevenness, repelling and the like, and a cured product of the resin composition. The purpose is to provide.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in order to achieve the above object, and as a result, (A) bonding oxide particles of a specific element with a specific organic compound containing a specific group. Particles comprising: (B) a compound having two or more polymerizable unsaturated groups in the molecule; and (C) at least two or more organic solvents having different relative evaporation rates. The present inventors have found that a resin composition containing a mixed solvent in which the difference between the maximum value and the minimum value is 1.5 or more and a cured product thereof can obtain one satisfying all the above-mentioned properties, and completed the present invention. . That is, the present invention provides the following resin compositions and cured products thereof.

[1] (A) oxide particles of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium, and a polymerizable unsaturated group; Particles formed by bonding to a specific organic compound containing a group represented by the following formula (1); (B) a compound having two or more polymerizable unsaturated groups in a molecule; and (C) at least two compounds having different relative evaporation rates. A resin composition comprising at least one kind of organic solvent, and a mixed solvent in which a difference between a maximum value and a minimum value of a relative evaporation rate of each organic solvent is 1.5 or more.

[0006]

Embedded image [In the formula (1), X represents NH, O (oxygen atom) or S (sulfur atom), and Y represents O or S. ]

[2] The specific organic compound is [-OC]
(= O) -NH-] group, and further contains [-OC (=
The resin composition according to the above [1], which contains at least one of an (S) -NH-] group and an [-SC (= O) -NH-] group.

[0008]

Embedded image [In the formula (1), X represents NH, O (oxygen atom) or S (sulfur atom), and Y represents O or S. ]

[3] The resin composition according to the above [1] or [2], wherein the specific organic compound is a compound having a silanol group or a compound which forms a silanol group by hydrolysis.

[4] The mixed solvent (C) contains an organic solvent having a relative evaporation rate of 1.5 or less.
The resin composition according to any one of [3].

[5] Among the organic solvents in the mixed solvent (C), the content of the organic solvent having the maximum value and the minimum value of the relative evaporation rate is 10% by weight based on 100% by weight of the mixed solvent (C). % Of the resin composition according to any one of [1] to [4].

[6] In addition to the above (A), (B) and (C), the above [1] to [D] further containing (D) a polymerization initiator.
The resin composition according to any one of [5].

[7] The polymerization initiator (D) is (d) 1
The resin composition according to the above [6], which is a radiation polymerization initiator containing both or any of an aryl ketone having a hydroxycyclohexyl group and an aryl ketone having an N-morpholino group. In the present invention, “radiation” refers to infrared rays, visible rays, ultraviolet rays, far ultraviolet rays, X rays.
Ray, electron beam, α ray, β ray, γ ray and the like.

[8] A cured product obtained by curing the resin composition according to any one of [1] to [7].

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the resin composition of the present invention and a cured product thereof will be specifically described. I. Resin Composition The resin composition of the present invention comprises (A) particles obtained by bonding oxide particles of a specific element and a specific organic compound containing a specific group (hereinafter referred to as “crosslinkable particles (A)”). ), (B) a compound having two or more polymerizable unsaturated groups in the molecule (hereinafter sometimes referred to as “compound (B)”), and (C) at least two compounds having different relative evaporation rates.
A mixed solvent containing at least one kind of organic solvent and having a difference between the maximum value and the minimum value of the relative evaporation rate of each organic solvent of 1.5 or more (hereinafter sometimes referred to as “mixed solvent (C)”); And, if necessary, (D) a polymerization initiator (for example, (d) 1
A radiation polymerization initiator containing both or any of an aryl ketone having a hydroxycyclohexyl group and an aryl ketone having an N-morpholino group).

Hereinafter, each composition (blending) component of the resin composition of the present invention will be specifically described. 1. Crosslinkable particles (A) The crosslinkable particles (A) used in the present invention are formed by oxidation of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium. Cross-linkable particles obtained by bonding a product particle with a specific organic compound containing a polymerizable unsaturated group and a group represented by the formula (1).

(1) Oxide Particles The oxide particles used in the present invention are preferably silicon, aluminum, zirconium, titanium, zinc, germanium, from the viewpoint of the colorlessness of the cured film of the obtained resin composition.
The oxide particles are at least one element selected from the group consisting of indium, tin, antimony, and cerium.

Examples of these oxides include silica, aluminum oxide, zirconia, titania, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), antimony oxide and cerium oxide. it can. Among them, silica, aluminum oxide, zirconia and antimony oxide are preferred from the viewpoint of high hardness. These can be used alone or in combination of two or more. Further, the oxide particles of such an element are preferably in the form of a powder or a solvent-dispersed sol. In the case of a solvent dispersion sol, the dispersion medium is preferably an organic solvent from the viewpoint of compatibility with other components and dispersibility. Examples of such an organic solvent include alcohols such as methanol, ethanol, isopropanol, butanol and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate and γ-butyrolactone. Esters such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; benzene, toluene,
Aromatic hydrocarbons such as xylene; amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like can be mentioned. Among them, methanol,
Isopropanol, butanol, methyl ethyl ketone,
Preferred are methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene and xylene.

The number average particle diameter of the oxide particles is 0.001.
μm to 2 μm, preferably 0.001 μm to 0.2 μm
Is more preferable, and 0.001 μm to 0.1 μm is particularly preferable. If the number average particle size exceeds 2 μm, the transparency of the cured product tends to decrease, and the surface state of the coating tends to deteriorate. Various surfactants and amines may be added to improve the dispersibility of the particles.

Silicon oxide particles (eg, silica particles)
As commercially available products, for example, as colloidal silica, Nissan Chemical Industries, Ltd. product name: methanol silica sol, IPA-ST, MEK-ST, NB
A-ST, XBA-ST, DMAC-ST, ST-U
P, ST-OUP, ST-20, ST-40, ST-
C, ST-N, ST-O, ST-50, ST-OL, and the like. As the powdered silica, trade names: Aerosil 130, Aerosil 300, Aerosil 380, Aerosil TT60 manufactured by Nippon Aerosil Co., Ltd.
0, Aerosil OX50, manufactured by Asahi Glass Co., Ltd. Brand name: Sildex H31, H32, H51, H52, H12
1, H122, manufactured by Nippon Silica Industry Co., Ltd. Product name: E2
20A, E220, manufactured by Fuji Silysia K.K.
YLYSIA470, manufactured by Nippon Sheet Glass Co., Ltd .: SG
Flakes and the like. Examples of the aqueous dispersion of alumina include alumina sol-100, -200, and -520 manufactured by Nissan Chemical Industries, Ltd .; and the dispersion of alumina with isopropanol includes Sumitomo Osaka Cement Co., Ltd.
Trade name: AS-150I; As a toluene dispersion of alumina, trade name: AS manufactured by Sumitomo Osaka Cement Co., Ltd.
-150T; As an aqueous dispersion of zinc antimonate powder, Nissan Chemical Industry Co., Ltd. product name: Celnax; As a powder and solvent dispersion of alumina, titanium oxide, tin oxide, indium oxide, zinc oxide and the like, C-I Kasei Co., Ltd.
Product name: Nanotech; antimony-doped tin oxide in water dispersion sol, manufactured by Ishihara Sangyo Co., Ltd .; product name: SN-1
00D; a product made by Mitsubishi Materials Corporation as the ITO powder; and a Neidral product name made by Taki Kagaku Co., Ltd. as the cerium oxide aqueous dispersion. The shape of the oxide particles is spherical, hollow, porous, rod-shaped, plate-shaped,
It is fibrous or irregular, preferably spherical.
The specific surface area of the oxide particles (based on a BET specific surface area measurement method using nitrogen) is preferably from 10 to 1000 m ² / g, and more preferably from 100 to 500 m ² / g. These oxide particles may be used in the form of dry powder,
Alternatively, it can be used in a state of being dispersed in water or an organic solvent. For example, a dispersion liquid of fine oxide particles known in the art as a solvent dispersion sol of the above oxide can be directly used. In particular, use of a solvent-dispersed sol of an oxide is preferred for applications requiring excellent transparency of the cured product.

(2) Specific Organic Compound The specific organic compound used in the present invention is a compound containing a polymerizable unsaturated group and a group represented by the above formula (1) in the molecule. Further, this compound is preferably a compound having a silanol group in the molecule or a compound capable of generating a silanol group by hydrolysis.

Polymerizable unsaturated group The polymerizable unsaturated group contained in the specific organic compound is not particularly limited. Examples thereof include an acryloyl group, a methacryloyl group, a vinyl group, a propenyl group, a butadienyl group, a styryl group, an ethynyl group, Cinnamoyl group, maleate group,
An acrylamide group can be mentioned as a preferred example.
This polymerizable unsaturated group is a structural unit that undergoes addition polymerization using an active radical species.

The group represented by the formula (1) The group represented by the formula (1) [—X
-C (= Y) -NH-] is, specifically, [-OC]
(= O) -NH-], [-OC (= S) -NH-],
[-SC (= O) -NH-], [-NH-C (= O)
-NH-], [-NH-C (= S) -NH-], and [-SC (= S) -NH-]. These groups can be used alone or in combination of two or more. Among them, from the viewpoint of thermal stability, [-OC
(= O) -NH-] group and [-OC (= S) -NH
It is preferable to use together with at least one of the-] group and the [-SC (= O) -NH-] group. The group [-XC (= Y) -NH-] represented by the above formula (1) generates an appropriate cohesive force due to hydrogen bonding between molecules, and when formed into a cured product, has excellent mechanical strength and group. It is considered that properties such as adhesion to the material and heat resistance are imparted.

Silanol group or group capable of forming silanol group by hydrolysis Specific organic compounds include compounds having a silanol group in the molecule (hereinafter sometimes referred to as "silanol group-containing compound") or hydrolysis. It is preferably a compound that generates a silanol group (hereinafter sometimes referred to as a “silanol group-forming compound”). Examples of such a silanol group-forming compound include compounds having an alkoxy group, an aryloxy group, an acetoxy group, an amino group, a halogen atom and the like on a silicon atom, and an alkoxy group or an aryloxy group on a silicon atom. A compound comprising
That is, an alkoxysilyl group-containing compound or an aryloxysilyl group-containing compound is preferable. The silanol group-generating site of the silanol group or the silanol group-generating compound,
It is a structural unit that bonds to the oxide particles by a condensation reaction or a condensation reaction that occurs following hydrolysis.

Preferred Embodiment Preferred specific examples of the specific organic compound include, for example, a compound represented by the following formula (2).

[0026]

Embedded image

In the formula (2), R ¹ and R ² may be the same or different and each is a hydrogen atom or a C ₁ to C ₈ alkyl or aryl group, for example, methyl, ethyl, propyl, butyl Octyl, phenyl, and xylyl groups. Here, m is 1, 2 or 3.

Examples of the group represented by _{^{[(R 1 O) m R}} 2 3-m Si-], for example, trimethoxysilyl groups, triethoxysilyl group, triphenoxysilyl group, methyldimethoxysilyl group, dimethylmethoxysilyl And the like. Among these groups, a trimethoxysilyl group or a triethoxysilyl group is preferred.

R ³ is a divalent organic group having a C ₁ to C ₁₂ aliphatic or aromatic structure, and may have a chain, branched or cyclic structure. Such organic groups include, for example, methylene, ethylene, propylene, butylene, hexamethylene, cyclohexylene, phenylene,
Xylylene, dodecamethylene and the like can be mentioned.
Preferred examples among these are methylene, propylene, cyclohexylene, phenylene and the like.

R ⁴ is a divalent organic group.
Molecular weight 14 to 10,000, preferably molecular weight 76 to 50
It is selected from 0 divalent organic groups. For example, chain-like polyalkylene groups such as hexamethylene, octamethylene and dodecamethylene; alicyclic or polycyclic divalent organic groups such as cyclohexylene and norbornylene; divalent organic groups such as phenylene, naphthylene, biphenylene and polyphenylene Aromatic groups; and substituted alkyl and aryl groups thereof. In addition, these divalent organic groups may include an atomic group containing an element other than carbon and hydrogen atoms, and include a polyether bond, a polyester bond, a polyamide bond, a polycarbonate bond, and a compound represented by the formula (1).
May be included.

R ⁵ is an (n + 1) -valent organic group, and is preferably selected from a chain, branched or cyclic saturated hydrocarbon group and an unsaturated hydrocarbon group.

Z represents a monovalent organic group having a polymerizable unsaturated group in the molecule which undergoes an intermolecular crosslinking reaction in the presence of an active radical species. For example, acryloyl (oxy) group, methacryloyl (oxy) group, vinyl (oxy) group, propenyl (oxy) group, butadienyl (oxy) group, styryl (oxy) group, ethynyl (oxy) group, cinnamoyl (oxy) group , Maleate group, acrylamide group, methacrylamide group and the like. Among these, an acryloyl (oxy) group and a methacryloyl (oxy) group are preferred. Further, n is preferably a positive integer of 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 5.

For the synthesis of the specific organic compound used in the present invention, for example, a method described in JP-A-9-100111 can be used. That is, the reaction can be carried out by (a) an addition reaction of a mercaptoalkoxysilane, a polyisocyanate compound, and an active hydrogen group-containing polymerizable unsaturated compound. In addition, (b) the reaction can be carried out by a direct reaction between a compound having an alkoxysilyl group and an isocyanate group in the molecule and an active hydrogen-containing polymerizable unsaturated compound. Furthermore, (c) the compound having a polymerizable unsaturated group and an isocyanate group in a molecule and a mercaptoalkoxysilane or an aminosilane can be directly synthesized by an addition reaction.

In order to synthesize the compound represented by the formula (2), (a) of these methods is suitably used.
More specifically, for example, the method (a): first reacting a mercaptoalkoxysilane with a polyisocyanate compound to form an alkoxysilyl group, a [—S—C (−O) —NH—] group and an isocyanate in the molecule. An intermediate containing a group is formed and then the isocyanate remaining in the intermediate is reacted with a hydroxy group-containing polymerizable unsaturated compound to convert the unsaturated compound into [-OC (= O) -NH A method of bonding via a-] group, method (b); a polyisocyanate compound and a hydroxy group-containing polymerizable unsaturated compound are first reacted to form a polymerizable unsaturated group, [-OC (= O) -NH-] group,
And forming an intermediate containing an isocyanate group, and reacting the intermediate with the mercaptoalkoxysilane to bond the mercaptoalkoxysilane via a [—S—C (＝ O) —NH—] group. Can be. Among them, the method (a) is preferable because there is no decrease in the polymerizable unsaturated group due to the Michael addition reaction.

In the synthesis of the compound represented by the formula (2), the reaction with an isocyanate group results in [-SC (=
Examples of the alkoxysilane capable of forming the O) —NH—] group include compounds having one or more alkoxysilyl groups and one or more mercapto groups in the molecule. Examples of such mercaptoalkoxysilanes include, for example, mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, mercaptopropylmethyldiethoxysilane, mercaptopropyldimethoxymethylsilane, mercaptopropylmethoxydimethylsilane, mercaptopropyltriphenoxysisilane, mercapto Propyl tributoxy silane can be exemplified. Of these, mercaptopropyltrimethoxysilane and mercaptopropyltriethoxysilane are preferred. Further, an addition product of an amino-substituted alkoxysilane and an epoxy-substituted mercaptan,
An addition product of an epoxysilane and an α, ω-dimercapto compound can also be used.

The polyisocyanate compound used in synthesizing the specific organic compound includes a chain saturated hydrocarbon,
It can be selected from polyisocyanate compounds composed of cyclic saturated hydrocarbons and aromatic hydrocarbons.

Examples of such polyisocyanate compounds include, for example, 2,4-tolylene diisocyanate
2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5-naphthalenedi isocyanate, m-phenylene diisocyanate P-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethylphenylene diisocyanate, 4,4′-biphenylene diisocyanate,
1,6-hexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), 2,2,4-trimethylhexamethylene diisocyanate, bis (2-isocyanate ethyl)
Fumarate, 6-isopropyl-1,3-phenyldiisocyanate, 4-diphenylpropanediisocyanate
, Lysine diisocyanate, hydrogenated diphenylmethane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, tetramethylxylylene diisocyanate, 2,5 (or 6) -bis (isocyanatomethyl ) -Bicyclo [2.2.1] heptane and the like. Among these, 2,4-tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, methylene bis (4-cyclohexyl isocyanate), 1,3-bis (isocyanatomethyl) cyclohexane, and the like are preferable. These can be used alone or in combination of two or more.

In the synthesis of the specific organic compound, the polyisocyanate compound is reacted with [-OC (=
Examples of the active hydrogen-containing polymerizable unsaturated compound that can be bonded via an O) —NH—] group include an [—O—C (＝ O) —NH—] group by an addition reaction with an isocyanate group in the molecule. A compound having at least one active hydrogen atom capable of forming a compound and having at least one polymerizable unsaturated group.

Examples of these active hydrogen-containing polymerizable unsaturated compounds include, for example, 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acryl
2-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate
Hydroxy-3-phenyloxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, 2-hydroxyalkyl (meth) acryloyl phosphate, 4-hydroxycyclohexyl (meth) acrylate 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, trimethylolpropane di (meth)
Acrylate, trimethylolethanedi (meth) acrylate, pentaerythritol tri (meth) acrylate
G, dipentaerythritol penta (meth) acryle
And the like. Further, a compound obtained by an addition reaction of a glycidyl group-containing compound such as alkyl glycidyl ether, allyl glycidyl ether, glycidyl (meth) acrylate and (meth) acrylic acid can be used. Among these compounds, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate and the like are preferable. These compounds can be used alone or as a mixture of two or more.

(3) Method for Producing Crosslinkable Particles (A) The method for producing the crosslinkable particles (A) of the present invention is not particularly limited. Can be mentioned. Oxide particles are known to contain moisture as adsorbed water on the particle surface in a normal storage state, and at least a component that reacts with a silanol group-forming compound such as a hydroxide or a hydrate is present on the surface. It is estimated to be. Therefore, at the time of producing the crosslinkable particles (A), it is also possible to produce the mixture by mixing a silanol group-forming compound and oxide particles, followed by heating and stirring. Note that the reaction is preferably performed in the presence of water in order to efficiently combine the silanol group generation site of the specific organic compound with the oxide particles. However, when the specific organic compound has a silanol group, water may not be necessary. Therefore, the crosslinkable particles (A)
It can be manufactured by a method including an operation of mixing at least the oxide particles and the specific organic compound.

Hereinafter, a method for producing the crosslinkable particles (A) will be described in detail. The amount of the specific organic compound bonded to the oxide particles is preferably 0.0% with respect to 100% by weight of the crosslinkable particles (A) (total of the oxide particles and the specific organic compound).
It is at least 1% by weight, more preferably at least 0.1% by weight, particularly preferably at least 1% by weight. When the amount of the specific organic compound bonded to the oxide particles is less than 0.01% by weight, the dispersibility of the crosslinkable particles (A) in the composition is not sufficient, and the transparency and the resistance of the obtained cured product are poor. The abrasion may not be sufficient. In addition, the mixing ratio of the oxide particles in the raw material at the time of producing the crosslinkable particles (A) is
Preferably it is 5 to 99% by weight, more preferably 1 to 99% by weight.
0 to 98% by weight.

Hereinafter, the method for producing the crosslinkable particles (A) will be described in more detail by taking the alkoxysilyl group-containing compound (alkoxysilane compound) represented by the formula (2) as an example of the silanol group-forming compound. The amount of water consumed in the hydrolysis of the alkoxysilane compound during the production of the crosslinkable particles (A) may be such that at least one of the alkoxy groups on silicon in one molecule is hydrolyzed. Preferably, the amount of water added or present during the hydrolysis is at least one third of the number of moles of all alkoxy groups on silicon, and more preferably one half of the number of moles of all alkoxy groups. More than three times. The product obtained by mixing the alkoxysilane compound and the oxide particles under completely water-free conditions is a product in which the alkoxysilane compound is physically adsorbed on the surface of the oxide particles, and is composed of such components. In the cured product of the composition containing the crosslinkable particles (A) to be obtained, the effect of exhibiting high hardness and scratch resistance is low.

In producing the crosslinkable particles (A), the alkoxysilane compound is separately subjected to a hydrolysis operation, and then mixed with powdered oxide particles or a solvent dispersion sol of oxide particles, and heated and stirred. A method of performing an operation; or a method of performing hydrolysis of the alkoxysilane compound in the presence of oxide particles; and a surface treatment of the oxide particles in the presence of another component such as (D) a polymerization initiator. Can be selected. Among these, a method in which the alkoxysilane compound is hydrolyzed in the presence of oxide particles is preferable. During the production of the crosslinkable particles (A), the temperature is preferably from 0 ° C. to 150 ° C., more preferably 20 ° C.
It is not less than 100 ° C and not more than 100 ° C. Processing times are typically in the range of 5 minutes to 24 hours.

When a powdery oxide powder is used in the production of the crosslinkable particles (A), an organic solvent is added for the purpose of smoothly and uniformly reacting with the alkoxysilane compound. You may. As such an organic solvent, the same solvent as that used as the dispersion medium of the solvent dispersion sol of the oxide particles can be used. The amount of these solvents to be added is not particularly limited as long as the reaction is carried out smoothly and uniformly.

When a solvent-dispersed sol is used as a raw material of the crosslinkable particles (A), it can be produced by mixing at least the solvent-dispersed sol and a specific organic compound. Here, an organic solvent that is uniformly compatible with water may be added for the purpose of ensuring uniformity in the initial stage of the reaction and smoothly proceeding the reaction.

In the production of the crosslinkable particles (A),
To promote the reaction, an acid, salt or base may be added as a catalyst. Examples of the acid include hydrochloric acid, nitric acid, sulfuric acid,
Inorganic acids such as phosphoric acid; organic acids such as methanesulfonic acid, toluenesulfonic acid, phthalic acid, malonic acid, formic acid, acetic acid, and oxalic acid; unsaturated organic acids such as methacrylic acid, acrylic acid, and itaconic acid; For example, ammonium salts such as tetramethylammonium hydrochloride and tetrabutylammonium hydrochloride, and bases such as primary, secondary and tertiary such as aqueous ammonia, diethylamine, triethylamine, dibutylamine and cyclohexylamine
And aromatic amines such as tertiary aliphatic amines and pyridine; and quaternary ammonium hydroxides such as sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide and tetrabutylammonium hydroxide. Among these, preferred examples of the acid are organic acids and unsaturated organic acids, and the bases are tertiary amines and quaternary ammonium hydroxides. These acids, salts or bases are added in an amount of preferably 0.001 to 1.0 parts by weight, based on 100 parts by weight of the alkoxysilane compound.
More preferably, the amount is 0.01 part by weight to 0.1 part by weight. It is also preferable to add a dehydrating agent to promote the reaction. As the dehydrating agent, inorganic compounds such as zeolite, anhydrous silica, and anhydrous alumina, and organic compounds such as methyl orthoformate, ethyl orthoformate, tetraethoxymethane, and tetrabutoxymethane can be used.
Among them, organic compounds are preferable, and orthoesters such as methyl orthoformate and ethyl orthoformate are more preferable. The amount of the alkoxysilane compound bonded to the crosslinkable particles (A) is usually 11% in air as a constant value of the weight loss% when the dry powder is completely burned in air.
It can be determined by thermogravimetric analysis from 0 ° C to 800 ° C.

The compounding amount of the crosslinkable particles (A) in the resin composition is determined according to the composition [crosslinkable particles (A) and compound (B)].
Is preferably 100% by weight, and 5 to 90% by weight is more preferable, and 10 to 70% by weight is more preferable. If it is less than 5% by weight, the hardness of the cured product may be insufficient, and if it exceeds 90% by weight, it may not be cured (not formed into a film). The amount of the crosslinkable particles (A) means a solid content, and when the crosslinkable particles (A) are used in the form of a solvent-dispersed sol, the compounding amount does not include the amount of the solvent.

2. Compound (B) The compound (B) used in the present invention is a compound containing two or more polymerizable unsaturated groups in a molecule. This compound (B)
Is preferably used to enhance the film formability of the composition. The compound (B) is not particularly limited as long as it contains two or more polymerizable unsaturated groups, and examples thereof include (meth) acrylic esters and vinyl compounds. Among them, (meth) acrylic esters are preferred.

Hereinafter, specific examples of the compound (B) used in the present invention will be listed. (Meth) acrylic esters include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate Acrylate, dipentaerythritol hexa (meth) acrylate, glycerin tri (meth) acrylate, tris (2
-Hydroxyethyl) isocyanurate tri (meth) acrylate, ethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate,
1,4-butanediol di (meth) acrylate, 1,
6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bis ( 2-hydroxyethyl) isocyanurate di (meth) acrylate, and poly (meth) acrylates of ethylene oxide or propylene oxide adducts to these starting alcohols;
Oligoester (meth) acrylates having two or more (meth) acryloyl groups in the molecule, oligoether (meth) acrylates, oligourethane (meth) acrylates, oligoepoxy (meth) acrylates, and the like. it can. Of these, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, and ditrimethylolpropanetetra (meth) acrylate are preferred.

Examples of the vinyl compounds include divinylbenzene, ethylene glycol divinyl ether, diethylene glycol divinyl ether, and triethylene glycol divinyl ether.

Commercially available compounds (B) include, for example, trade names: Aronix M-400, M-408, M-450, M-305, manufactured by Toagosei Co., Ltd.
M-309, M-310, M-315, M-320,
M-350, M-360, M-208, M-210, M
-215, M-220, M-225, M-233, M-
240, M-245, M-260, M-270, M-1
100, M-1200, M-1210, M-1310,
M-1600, M-221, M-203, TO-92
4, TO-1270, TO-1231, TO-595,
TO-756, TO-1231, TO-1343, TO
-902, TO-904, TO-905, TO-133
0, manufactured by Nippon Kayaku Co., Ltd. Product name: KAYARAD D-
310, D-330, DPHA, DPCA-20, DP
CA-30, DPCA-60, DPCA-120, DN
-0075, DN-2475, SR-295, SR-3
55, SR-399E, SR-494, SR-904
1, SR-368, SR-415, SR-444, SR
-454, SR-492, SR-499, SR-50
2, SR-9020, SR-9035, SR-111,
SR-212, SR-213, SR-230, SR-2
59, SR-268, SR-272, SR-344, S
R-349, SR-601, SR-602, SR-61
0, SR-9003, PET-30, T-1420, G
PO-303, TC-120S, HDDA, NPGD
A, TPGDA, PEG400DA, MANDA, HX
-220, HX-620, R-551, R-712, R
-167, R-526, R-551, R-712, R-
604, R-684, TMPTA, THE-330, T
PA-320, TPA-330, KS-HDDA, KS
-TPGDA, KS-TMPTA, Kyoeisha Chemical Co., Ltd. Product name: Light Acrylate PE-4A, DPE-
6A and DTMP-4A.

The compounding amount of the compound (B) used in the present invention may be 10 to 95% by weight based on 100% by weight of the composition [total of the crosslinkable particles (A) and the compound (B)]. Preferably, 30 to 90% by weight is more preferable.
If the amount is less than 10% by weight, the cured product may have insufficient hardness. If the amount is more than 95% by weight, the cured product may have insufficient curl. In the composition of the present invention, a compound having one polymerizable unsaturated group in the molecule may be contained, if necessary, in addition to the compound (B).

3. Mixed solvent (C) The mixed solvent (C) used in the present invention contains at least two or more organic solvents having different relative evaporation rates, and the difference between the maximum value and the minimum value of the relative evaporation rates of each organic solvent is 1. 5 or more,
The mixed solvent is preferably 1.7 or more, more preferably 2.0 or more. When only one kind of organic solvent is used in place of the mixed solvent (C) used in the present invention, if the relative evaporation rate is high, the organic solvent after coating will evaporate quickly, resulting in wind ripples, streaks, repelling, etc. When the relative evaporation rate is low,
The organic solvent remains in the coating film, and the hardness of the cured product tends to be insufficient. Further, if the difference between the maximum value and the minimum value of the relative evaporation rate of each organic solvent is less than 1.5 even in a mixed solvent containing two or more organic solvents,
The same problem as when only a kind of organic solvent is used is likely to occur. In addition, the mixed solvent (C) used in the present invention preferably contains an organic solvent having a relative evaporation rate of 1.5 or less, and more preferably contains an organic solvent having a relative evaporation rate of 1.0 or less. By containing an organic solvent having a relative evaporation rate of 1.5 or less, it is possible to obtain an appropriate solvent evaporation rate for forming a coating film without poor appearance.

Here, as shown in the following equation (3), the relative evaporation rate is determined by the measurement method described in ASTM D3539-87.
It is defined as the ratio of the evaporation time of butyl to the evaporation time of each organic solvent. The relative evaporation rate of each organic solvent is
This is described in Table 5 on pages 17 to 19 of "Latest Coating Technology" (issued by Sogo Gijutsu Center in 1983).

[0055]

Relative evaporation rate = (time required for 90% by weight of n-butyl acetate to evaporate) / (time required for 90% by weight of the test solvent to evaporate) (3)

The mixing amount of the mixed solvent (C) in the resin composition is preferably 5 to 9900 parts by weight, based on 100 parts by weight of the composition [total of the crosslinkable particles (A) and the compound (B)]. Is 20 to 2000 parts by weight, more preferably 25
２０００2000 parts by weight. If the amount is less than 5 parts by weight, poor appearance of the coating film surface may occur. If the amount exceeds 9900 parts by weight, a sufficient film thickness may not be obtained.

The content of the organic solvent having the maximum value and the minimum value of the relative evaporation rate among the organic solvents in the mixed solvent (C) is 10% by weight or more with respect to the mixed solvent (C) being 100% by weight. It is preferred that If the amount of the organic solvent having the maximum relative evaporation rate is less than 10% by weight, the drying time may be long. If the amount of the organic solvent having the minimum relative evaporation rate is less than 10% by weight, uneven coating and repelling may occur. This may cause poor appearance of the coating film surface, such as wind ripples and streaks.

As specific examples of the mixed solvent (C), a mixed solvent of methyl ethyl ketone (relative evaporation rate: 3.7) / isopropanol (1.5), a mixed solvent of methyl ethyl ketone / toluene (2.0), methyl ethyl ketone / cyclohexanone (0.32) Mixed solvent, methanol (1.9) / cyclohexanone mixed solvent, methyl isobutyl ketone (1.6) / methanol mixed solvent, methyl ethyl ketone / methanol mixed solvent, methyl ethyl ketone / methyl isobutyl ketone / isopropanol mixed solvent And a mixed solvent of methyl ethyl ketone / methyl isobutyl ketone / cyclohexanone, a mixed solvent of methyl ethyl ketone / methyl isobutyl ketone / methanol / isopropanol, and the like.

4. Polymerization Initiator (D) In the composition of the present invention, if necessary, (D) a polymerization initiator may be used as a compounding component other than the crosslinkable particles (A), the compound (B) and the mixed solvent (C). Can be blended. First, including the use of the (D) polymerization initiator,
The method for curing the composition of the present invention will be described.

The compositions of the present invention are cured by heat and / or radiation. When using heat, for example, an electric heater, an infrared lamp, hot air or the like can be used as the heat source. In the case of radiation, the radiation source is not particularly limited as long as the composition can be cured in a short time after coating, but as the infrared radiation source, for example, a lamp, a resistance heating plate, Lasers, etc., as visible light sources, for example, sunlight, lamps, fluorescent lamps, lasers, etc., and as UV ray sources, for example, mercury lamps, halide lamps, lasers, etc. As the radiation source, for example, a system using thermoelectrons generated from a commercially available tungsten filament, a cold cathode system generated by applying a high voltage pulse to a metal, and a system generated by collision of ionized gaseous molecules with a metal electrode 2 A secondary electron system using a secondary electron can be used. Alpha, base - as a source of data lines and gamma rays, for example, include fissile material, such as Co ^60, for gamma rays can utilize a vacuum tube or the like which causes accelerated electrons to collide with an anode. These radiations may be irradiated alone or in combination of two or more, or one or more radiations may be irradiated at a fixed time interval. A polymerization initiator (D) may be added to the composition of the present invention in order to shorten the curing time, and such a polymerization initiator (D), for example, generates an active radical species thermally. Commonly used compounds such as compounds and compounds that generate active radical species upon irradiation with radiation can be mentioned.

In the present invention, a radiation polymerization initiator is preferably used as the polymerization initiator (D), and among them, (c) aryl ketones having a 1-hydroxycyclohexyl group and aryl ketones having an N-morpholino group It is more preferable to use a radiation polymerization initiator containing both or either of ketones (hereinafter, sometimes referred to as “radiation polymerization initiator (d)”). When only an aryl ketone having a 1-hydroxycyclohexyl group is added, a cured product with less coloring can be formed in a short time. On the other hand, when only an aryl ketone having an N-morpholino group is added, a cured product having a high surface hardness can be formed in a short time. When both are used together, a cured product having high surface hardness and little coloring can be formed in a short time.

The aryl ketone having a 1-hydroxycyclohexyl group is not particularly limited.
1-hydroxycyclohexyl phenyl ketone, 1-hydroxycyclohexyl isopropyl phenyl ketone, 1
-Hydroxycyclohexyl decyl phenyl ketone. The N- used in the present invention
The aryl ketone having a morpholino group is not particularly limited. For example, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1,2-methyl-1- [4- ( Methoxy) phenyl] -2-morpholinopropanone-1,2-methyl-1- [4- (2-hydroxyethoxy) phenyl] -2-morpholinopropanone-1,2-methyl-1- [4- (dimethyl Amino) phenyl] -2-morpholinopropanone-1,2-methyl-1- [4- (diphenylamino) phenyl] -2-morpholinopropanone-1,2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) -butanone-1,3,6-bis (2-methyl-2-morpholinopropionyl) -9-N-octylcarbazole. These radiation polymerization initiators (d) may be used alone or in combination of two or more.
In order to improve the curing speed and hardness of both the surface portion and the interior of the cured product, an aryl ketone having a 1-hydroxycyclohexyl group and an aryl ketone having an N-morpholino group are combined. It is preferable to use them. Commercial products of such a radiation polymerization initiator (d) include, for example, Irgacure 18 manufactured by Ciba Specialty Chemicals Co., Ltd.
4, 907 and the like.

The compounding amount of the radiation polymerization initiator (d) used as required in the present invention is 0. 0 to 100 parts by weight of the composition [total of the crosslinkable particles (A) and the compound (B)]. It is preferred that the compounding amount be from 01 to 20 parts by weight,
0.1 to 10 parts by weight is more preferred. If the amount is less than 0.01 part by weight, the hardness of the cured product may be insufficient. If the amount is more than 20 parts by weight, the cured product may not be hardened to the inside (lower layer).

When an aryl ketone having a 1-hydroxycyclohexyl group and an aryl ketone having an N-morpholino group are used in combination, the mixing ratio of both is preferably from 10:90 to 90:10 by weight. 40: 6
0 to 80:20 is more preferable.

5. Ingredients other than those described above In the present invention, various ingredients other than those described above, such as a sensitizer, oxide particles other than the crosslinkable particles (A), and various additives, can be incorporated as necessary. Hereinafter, examples are listed. (1) Sensitizer Examples of the sensitizer include triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, -Isoamyl dimethylaminobenzoate. Commercial products of this sensitizer include KAYACURE DMBI, EP, manufactured by Nippon Kayaku Co., Ltd.
A and the like.

(2) Oxide particles other than the crosslinkable particles (A) Examples of the oxide particles other than the crosslinkable particles (A) include:
Oxide particles that are not bonded to a specific organic compound can be given.

(3) Various additives Examples of the additives include an antioxidant, an ultraviolet absorber, a light stabilizer, a silane coupling agent, an antioxidant, a thermal polymerization inhibitor, a coloring agent, a leveling agent, and a surfactant. And storage stabilizers, plasticizers, lubricants, inorganic fillers, organic fillers, fillers, wettability improvers, coating surface improvers, and the like.

Commercial products of antioxidants include Irganox 1010, 1035, 1076 and 1222 (trade names, manufactured by Ciba Specialty Chemicals Co., Ltd.). Examples of ultraviolet absorbers include Ciba Specialty Chemicals. Chemicals Corporation product name: Tinuvin P, 23
4, 320, 326, 327, 328, 213, 40
0, manufactured by Sumitomo Chemical Co., Ltd. Product name: Sumisorb 11
0, 130, 140, 220, 250, 300, 32
0, 340, 350, 400 and the like. Commercially available light stabilizers are trade names of Tinuvin 292, 144, 62 manufactured by Ciba Specialty Chemicals Co., Ltd.
2LD, manufactured by Sankyo Chemical Industry Co., Ltd. Product name: SANOL LS
−770, 765, 292, 2626, 1114, 74
4 and the like, and examples of the silane coupling agent include γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane.
These commercially available products are trade names: SH6062, SZ603 manufactured by Dow Corning Toray Silicone Co., Ltd.
0, manufactured by Shin-Etsu Silicone Co., Ltd.
KBM803 and the like, and as a commercially available anti-aging agent, brand name: Antigen W, S, P, 3C, 6C, RD-G, FR, AW, etc., manufactured by Sumitomo Chemical Co., Ltd. it can.

(4) Additives Other than the Above Additives other than the above include epoxy resin, polyamide, polyimide, polyamideimide, polyurethane, polybutadiene, chloroprene, polyether, polyester, pentadiene derivative, styrene / butadiene / styrene block copolymer. Polymer, styrene / ethylene / butene / styrene block copolymer, styrene / isoprene /
Styrene block copolymer, petroleum resin, xylene resin,
Examples include polymers or oligomers such as ketone resins, fluorine oligomers, silicone oligomers, and polysulfide oligomers.

The composition of the present invention is suitable as a coating material. Examples of the substrate to be coated include plastics (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, Triacetyl cellulose, ABS, AS, norbornene resin, etc.), metal, wood, paper, glass, thread
And the like. The shape of these substrates is plate-like,
It may be in the form of a film or a three-dimensional molded product, and the coating method may be a usual coating method, for example, dipping coat, spray coat, flow coat, shower coat.
G, roll coating, spin coating, brush coating, and the like. The thickness of the coating in these coatings after drying and curing is usually 0.1 to 400 μm, preferably 1 to 200 μm.

The composition of the present invention can be used after being diluted with a solvent in order to adjust the thickness of the coating film. For example,
When used as a coating material, the viscosity is usually 0.1 to 50,
000 mPa · s / 25 ° C., preferably 0.5 to
It is 10,000 mPa · s / 25 ° C.

II. Cured Product The cured product of the present invention can be obtained by coating the resin composition on various substrates, for example, a plastic substrate and curing the resin composition. Specifically, the composition can be obtained by coating the composition, preferably drying the volatile components at 0 to 200 ° C., and then performing a curing treatment with heat or / and radiation. Preferred curing conditions in the case of heat are 20 to 150 ° C., and 10 seconds to
Performed within 24 hours. When using radiation, it is preferable to use ultraviolet rays or electron beams. In such a case, the preferable irradiation amount of ultraviolet light is 0.01 to 10 J / c.
m ² , more preferably 0.1 to ² J / cm ² . In addition, preferable electron beam irradiation conditions are as follows.
0 to 300 KV, electron density 0.02 to 0.30 mA / c
m ^2, and the electron beam dose is 1～10Mrad.

The cured product of the present invention has excellent properties such as hardness, scratch resistance, low curl, adhesion, transparency and appearance of the coating surface, especially the appearance of the coating surface. , Plastic optical parts, touch panels, film-type liquid crystal elements, plastic containers, floor coverings, wall coverings, artificial marble, etc. It is suitably used as a hard coat material for plastic sheets, plastic films, and the like, which require the following.); Adhesives for various substrates, sealing materials; binder materials for printing inks, and the like.

[0074]

EXAMPLES The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples. In the following, parts and% indicate parts by weight and% by weight, respectively, unless otherwise specified. In the present invention, the “solid content” means a portion obtained by removing a volatile component such as a solvent from the composition, and specifically, is obtained by drying the composition on a hot plate at 120 ° C. for 1 hour. It means a residue (non-volatile component).

Synthesis of Specific Organic Compound Synthesis Example 1 A solution consisting of 7.8 parts of mercaptopropyltrimethoxysilane and 0.2 parts of dibutyltin dilaurate in dry air was stirred at 50 ° C. while stirring 20.6 parts of isophorone diisocyanate. At 60 ° C. for 3 hours.
Stirred for hours. To this, 71.4 parts of pentaerythritol triacrylate was added dropwise at 30 ° C. over 1 hour.
The specific organic compound (S1) is obtained by heating and stirring at 3 ° C. for 3 hours.
I got The infrared absorption spectrum of the product is shown by the absorption peak of 2550 Kaiser characteristic of the mercapto group and the absorption peak of 2260 Kaiser characteristic of the isocyanate group in the raw material.
The 1660 Kaiser peak characteristic of the carbonyl in the [-OC (= O) -NH-] and [-SC (= O) -NH-] groups disappears. And a peak of 1720 Kaiser characteristic of an acryloyl group were observed, and an acryloyl group as a polymerizable unsaturated group and [-SC (=
It was shown that a specific organic compound having both an [O) -NH-] group and a [-OC (= O) -NH-] group was generated.

Synthesis Example 2 Mercaptopropyltrimethoxysilane 3 in dry air
To a solution consisting of 8.4 parts and 0.2 parts of dibutyltin dilaurate, 38.7 parts of 1,3-bis (isocyanatomethyl) cyclohexane was added dropwise with stirring at 50 ° C. for 1 hour. The mixture was heated and stirred at ℃ for 3 hours. This is 2
After dropping 22.7 parts of -hydroxyethyl acrylate over 1 hour at 30 ° C, the mixture was heated and stirred at 60 ° C for 10 hours to obtain a specific organic compound (S2). Analysis of the amount of residual isocyanate in the product was less than 0.1%.
It indicated that the reaction was almost quantitatively completed.

Production of Crosslinkable Particles (A) Hereinafter, Production Examples of the crosslinkable particles (A) are shown in Production Examples 1 to 4, and the results are summarized in Table 1. Production Example 1 The specific organic compound (S) synthesized in Synthesis Example 1 under a nitrogen stream
1) 8.7 parts, 91.3 parts of methyl ethyl ketone silica sol (manufactured by Nissan Chemical Industries, Ltd., trade name: MEK-ST, number average particle diameter: 0.022 μm, silica concentration 30%), 0.2 parts of isopropanol, and ions After stirring a mixture of 0.1 part of exchanged water at 80 ° C. for 3 hours, 1.4 parts of orthoformic acid methyl ester was added, and the mixture was further heated and stirred at the same temperature for 1 hour to obtain colorless and transparent crosslinkable particles (A ) A dispersion (dispersion a) was obtained. After weighing 2 g of the dispersion a in an aluminum dish,
After drying on a hot plate at 1 ° C. for 1 hour and weighing, the solid content was determined to be 35%.

Production Example 2 The specific organic compound (S) synthesized in Synthesis Example 2 under a nitrogen stream
2) 8.3 parts of the above methyl ethyl ketone silica sol (M
After stirring a mixed solution of 91.7 parts of EK-ST and 0.8 parts of ion-exchanged water at 80 ° C. for 3 hours, 4.9 parts of orthoformic acid methyl ester was added, and the same temperature (80 hours) was further added for 1 hour.
C.) to obtain translucent crosslinkable particle (A) dispersion (dispersion b). The solid content of this dispersion liquid b was determined in the same manner as in Production Example 1 to be 34%.

Production Example 3 4.8 parts of the specific organic compound (S1) synthesized in Synthesis Example 1,
Isopropanol alumina sol (manufactured by Sumitomo Osaka Cement Co., Ltd., trade name: AS-150I, number average particle size: 0.1
95.2 parts, 0.01 parts of p-methoxyphenol, and 0.1 parts of ion-exchanged water.
Part of the mixture was stirred at 60 ° C. for 3 hours, then 1.0 part of orthoformic acid methyl ester was added, and the mixture was further heated and stirred at the same temperature for 1 hour to obtain a dispersion of the crosslinkable particles (A) (dispersion c). Obtained. The solid content of this dispersion c was determined in the same manner as in Production Example 1, and found to be 19%.

Production Example 4 8.2 parts of the specific organic compound (S1) synthesized in Synthesis Example 1,
Toluene zirconia sol (number average particle size 0.01 μm,
(Zirconia concentration 30%) 91.8 parts, ion exchange water 0.1
After stirring for 3 hours at 60 ° C., 1.3 parts of orthoformic acid methyl ester and 41.2 parts of methyl ethyl ketone were added, and the mixture was further heated and stirred at the same temperature for 1 hour to disperse the crosslinkable particles (A). A liquid (dispersion d) was obtained. This dispersion d
Was determined in the same manner as in Production Example 1 and found to be 25%.

[0081]

[Table 1] P1: Methyl ethyl ketone silica sol (oxide concentration 30
%) P2: isopropanol alumina sol (oxide concentration 15
%) P3: toluene zirconia sol (oxide concentration 30%)

Preparation Examples of Compositions Hereinafter, preparation examples of the composition of the present invention are shown in Examples 1 to 5, and comparative examples are shown in Comparative Examples 1 and 2. Table 2 shows the weight ratio of each component.

Example 1 In a 500 cc eggplant-shaped flask, 151 parts of the dispersion a prepared in Production Example 1 (53 parts of crosslinkable particles, dispersion medium methyl ethyl ketone (MEK)), 23.5 parts of dipentaerythritol hexaacrylate, and pentane After adding and mixing 23.5 parts of erythritol tetraacrylate, the mixture was concentrated under reduced pressure to 131 parts using a rotary evaporator, and then methyl isobutyl ketone (MIBK) 122 was added.
Part, 1-hydroxycyclohexyl phenyl ketone
9 parts and 0.9 part of 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropanone-1 were stirred at 50 ° C. for 2 hours to obtain a uniform solution composition. This preparation was performed in a room shielded from ultraviolet rays.
The solid content of this composition was determined in the same manner as in Production Example 1, and found to be 40%.

Example 2 A composition of Example 2 was obtained in the same manner as in Example 1, except that the composition was changed to the composition shown in Table 2.

Example 3 151 parts of the dispersion b prepared in Production Example 2 (crosslinkable particles 53) were placed in a container protected from ultraviolet light under a stream of dry air.
Parts, dispersing medium methyl ethyl ketone (MEK)), dipentaerythritol hexaacrylate 23.5 parts, pentaerythritol tetraacrylate 23.5 parts, cyclohexanone 55 parts, 1-hydroxycyclohexyl phenyl ketone 0.9 part, and 2- Methyl-1- (4- (methylthio) phenyl) -2-morpholinopropanone-
By stirring 10.9 parts at 50 ° C. for 2 hours, a uniform solution composition was obtained. Production Example 1
When it was determined in the same manner as in the above, it was 40%.

Examples 4 to 5 and Comparative Examples 1 and 2 The compositions of Examples 4 to 5 and Comparative Examples 1 and 2 were prepared in the same manner as in Example 3 except that the compositions shown in Table 2 were used. Obtained.

Evaluation of Cured Product In order to clarify the effect of the composition of the present invention, a cured product obtained by applying, drying and irradiating the above composition was evaluated. The evaluation method is described below. Table 2 shows the evaluation results.

1. Coating, drying, and curing conditions In Examples 1 to 4 and Comparative Examples 1 and 2 in Table 2, after applying on a substrate using a bar coater to a dry film thickness of 10 µm, a hot-air method of 80 ° C was used. After drying in a drier for 3 minutes, irradiation was performed at a light amount of 1 J / cm ² using a conveyer type mercury lamp, and after storage at 25 ° C. for 24 hours, evaluation was performed. The application conditions for the wind print test and the streak test are described separately.

2. Substrate A glass plate was used for the pencil hardness test, and a polyethylene terephthalate (PET) film having a thickness of 188 μm was used for the evaluation of the scratch resistance to steel wool, the evaluation of the adhesion, the curl, the wind print test, and the streak test.

3. Evaluation method-Pencil hardness: A cured film on a glass substrate was evaluated according to JIS K5400. Adhesion (%): Evaluated based on the cross-cut cellophane tape peeling test in JIS K5400, 1 mm square, remaining film ratio in a total of 100 cross-cuts.・ Steel wool (SW) scratch resistance: 30 reciprocations of # 0000 steel wool with a load of 500 g were performed on a Gakushin-type abrasion tester manufactured by Tester Sangyo Co., Ltd. for 30 times to check the scratched state of the tested coating film surface. It was evaluated visually. The case without scratches was evaluated as ○, the case with 1 to 10 scratches as Δ, and the case with more than 10 scratches as X. Wind test: After applying a dry film thickness of 10 μm on the PET using a bar coater, the coating film surface is blown with a cooling fan (wind speed 5 m / sec) for 2 minutes. Then 8
After drying in a hot-air dryer at 0 ° C. for 3 minutes, the film was irradiated with a light amount of 1 J / cm ² using a conveyor-type mercury lamp, and the degree of disorder of the coating film was visually observed. ○, when there is no abnormality in the coating film
The presence or absence of one or more foreign substances or the occurrence of abnormalities such as uneven coating, repelling, and devitrification was evaluated as x. Streak test: 1 ml of the composition of the present invention is dropped on PET at a width of 10 cm. After leaving it at room temperature for 2 minutes, it was applied to a dry film thickness of 10 μm using a bar coater, dried in a hot-air dryer at 80 ° C. for 3 minutes, and then dried at 1 J / cm ² using a conveyor-type mercury lamp. Irradiate with light to obtain a cured product. The degree of disturbance of the coating film is visually observed, and when the coating film has no trace of the bar coater, the case where the trace of the bar coater is 1 cm or more and less than 3 cm is Δ, and when the trace of the bar coater is 3 cm or more, ×. did.

[0091]

[Table 2] M1: dipentaerythritol hexaacrylate M2: pentaerythritol tetraacrylate R1: 1-hydroxycyclohexyl phenyl ketone R2: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1

[0092]

As described above, according to the present invention,
It has excellent coating properties, and has hardness, scratch resistance, low curl, adhesion, transparency, and appearance of the coating surface, especially on the surface of various base materials, especially wind ripples, streaks, uneven coating, repelling, etc. The present invention can provide a resin composition capable of forming a coating film having excellent coating film surface appearance and a cured product of the resin composition.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yuichi Eriyama 2-11-24 Tsukiji, Chuo-ku, Tokyo JAE SRL Inc. (72) Inventor Isao Nishiwaki 2-11-24 Tsukiji, Chuo-ku, Tokyo Jae (72) Inventor Takashi Ukaji 2-11-24 Tsukiji, Chuo-ku, Tokyo JAE F-term in SR Co., Ltd.

Claims (8)

[Claims] (A) An oxide particle of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium, and a polymerizable unsaturated group and Particles obtained by bonding a specific organic compound containing a group represented by the formula (1), (B) a compound having two or more polymerizable unsaturated groups in a molecule, and (C) at least two kinds having different relative evaporation rates. A resin composition comprising the above organic solvent and a mixed solvent in which a difference between a maximum value and a minimum value of a relative evaporation rate of each organic solvent is 1.5 or more. Embedded image [In the formula (1), X represents NH, O (oxygen atom) or S (sulfur atom), and Y represents O or S. ] 2. The method according to claim 1, wherein the specific organic compound is [-OC (=
O) -NH-] group, and further comprises [-OC (= S)
The resin composition according to claim 1, wherein the resin composition contains at least one of a -NH-] group and a -S-C (= O) -NH-] group. 3. The resin composition according to claim 1, wherein the specific organic compound is a compound having a silanol group or a compound which forms a silanol group by hydrolysis. 4. The resin composition according to claim 1, wherein the mixed solvent (C) contains an organic solvent having a relative evaporation rate of 1.5 or less. 5. The content of the organic solvent having a maximum value and a minimum value of the relative evaporation rate among the organic solvents in the mixed solvent (C) is 10% by weight with respect to 100% by weight of the mixed solvent (C). The resin composition according to any one of claims 1 to 4, which is the above. 6. In addition to the above (A), (B) and (C),
The resin composition according to any one of claims 1 to 5, further comprising (D) a polymerization initiator. 7. Radiation polymerization initiation wherein (D) the polymerization initiator contains (d) an aryl ketone having a 1-hydroxycyclohexyl group and / or an aryl ketone having an N-morpholino group. Claim 6 which is an agent.
3. The resin composition according to item 1. 8. A cured product obtained by curing the resin composition according to claim 1.